The use of supported rhodium nanoparticles (RhNPs) is gaining attention due to the drive for better catalyst performance and sustainability. Silica-based supports are promising for RhNP immobilization because of their thermal and chemical stability. Functionalizing silica allows for the design of catalysts with improved activity for biomass transformations. In this study, we synthesized rhodium nanoparticles (RhNPs) supported on N-functionalized silica-based materials, utilizing SBA-15 as the support and functionalizing it with either nicotinamide or an imidazolium-based ionic liquid. Solid-state ²⁹Si and ¹³C NMR experiments confirmed successful ligand anchoring onto the silica surface. RhNPs@SBA-15-Imz[NTf₂] and RhNPs@SBA-15-NIC were efficiently prepared and extensively characterized, revealing small, spherical, and well-dispersed fcc Rh nanoparticles on the support surface, confirmed by XPS analyses detecting metallic rhodium, Rh(I), and Rh(III) species. The catalytic performance of these materials is assessed in the hydrogenation of biomass-derived substrates, including furfural, levulinic acid, terpenes, vanillin, and eugenol, among others, underscoring their potential in sustainable chemical transformations. The nanocatalysts demonstrated excellent recyclability and resistance to metal leaching over multiple cycles. The study shows that neutral and ionic silica grafting fragments differently stabilize RhNPs, affecting their morphology, size, and interaction with silanol groups, which impacts their catalytic activity.

中文翻译：

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在功能化介孔二氧化硅上负载的铑纳米颗粒上的生物质衍生底物氢化


由于对更好的催化剂性能和可持续性的追求，负载型铑纳米颗粒 （RhNPs） 的使用越来越受到关注。二氧化硅基载体因其热稳定性和化学稳定性而有望用于 RhNP 固定化。功能化二氧化硅可以设计出具有更高生物质转化活性的催化剂。在这项研究中，我们合成了负载在 N 功能化二氧化硅基材料上的铑纳米颗粒 （RhNPs），利用 SBA-15 作为载体，并用烟酰胺或咪唑基离子液体对其进行功能化。固态 ²⁹Si 和 ¹³C NMR 实验证实配体成功锚定到二氧化硅表面。RhNPs@SBA-15-Imz[NTf₂] 和 RhNPs@SBA-15-NIC 被有效地制备和广泛表征，在支撑表面上揭示了小的、球形的、分散良好的 fcc Rh 纳米颗粒，XPS 分析检测金属铑、Rh（） 和 Rh（III） 物种证实了这一点。这些材料的催化性能在生物质衍生底物（包括糠醛、乙酰丙酸、萜烯、香兰素和丁香酚等）的氢化中进行评估，强调了它们在可持续化学转化中的潜力。纳米催化剂在多个循环中表现出优异的可回收性和抗金属浸出性。研究表明，中性和离子二氧化硅接枝片段对 RhNP 的稳定性不同，影响其形态、大小以及与硅醇基团的相互作用，从而影响其催化活性。